Journal of Analytical Methods in Chemistry

Research Article

Chemical Fingerprint and Metabolic Profile Analysis of Tianshu Tablets by Ultra-High Performance Liquid Chromatography/Quadrupole-Time of Flight Mass Spectrometry

Table 1

The chemical constituents detected from TST.


Peak	RT (min)	Formula	Error (ppm)	[M−H]⁻ (m/z)		Intensity	Product ions	Identification	Structure class	Ref.
Peak	RT (min)	Formula	Error (ppm)	Calculated	Measure	Intensity	Product ions	Identification	Structure class	Ref.

X1^a	0.98	C₇H₁₂O₆	−1.2	191.0561	191.0559	86129	154.9973, 127.0393, 111.0091, 93.0355, 85.0302, 73.0302	Quinic acid	Organic acids	[10]
X2	1.07	C₆H₈O₇	0.9	191.0197	191.0199	421357	111.0096, 87.0103	Citric acid	Organic acids	[10]
X3^b	1.07	C₉H₁₂N₂O₆	−1	243.0623	243.0620	5161	nd	Uridine	Nitrogen-containing compounds
X4^b	1.08	C₅H₇NO₃	3	128.0353	128.0357	24352	nd	Pyroglutamic acid	Organic acids
X5^b	1.36	C₆H₆O₄	1.1	141.0193	141.0195	3248	nd	5-(Hydroxymethyl)furoic acid	Organic acids	[11]
X6	1.36	C₁₀H₁₃N₅O₅	2.4	282.0844	282.0851	1153	150.0412, 133.0158, 108.0286	Guanosine	Nitrogen-containing compounds
X7	1.63	C₁₃H₁₈O₇	−1.1	285.0980	285.0977	1505	223.0248, 123.0432, 105.0348	Gastrodin	Glycosides	[12]
X8	2.03	C₇H₆O₄	0.7	153.0193	153.0195	16114	109.0300, 91.0193, 65.0057	Protocatechuic acid	Organic acids	[13]
X9	4.02	C₇H₆O₃	2.5	137.0244	137.0248	31464	119.0140, 108.0215, 93.0350, 81.0366, 65.0414	3,4-Dihydroxy benzaldehyde	Phenols	[14]
X10	4.70	C₁₉H₂₄O₁₃	1.7	459.1144	459.1152	283440	423.0939, 397.1138, 173.0088, 61.0444, 129.0184, 111.0088	Parishin E or G	Glycosides	[12]
X11	5.09	C₁₆H₁₈O₉	0.8	353.0878	353.0881	109164	191.0559, 173.0444, 161.0236, 134.0387, 111.0458, 93.0350, 85.0301	4-Caffeoylquinic acid	Organic acids	[15]
X12	5.13	C₁₇H₂₃N₃O₇S	0.5	412.1184	412.1186	11210	306.0753, 272.0898, 179.0459, 160.0077, 143.0461, 128.0348, 99.0559	S-(4-Hydroxybenzyl)-glutathione	Nitrogen-containing compounds	[12]
X13	5.24	C₂₃H₃₃N₃O₁₂S	2.3	574.1712	574.1726	7677	484.1388, 378.0974, 306.0756, 272.0874, 210.0864, 143.0464	S-(4-Hydroxybenzyl)-glutathione glucoside	Nitrogen-containing compounds
X14	5.34	C₉H₁₀O₄	−0.2	181.0506	181.0506	2573	136.9210, 121.0296, 109.0279	4-(2-Hydroxyethoxy)benzoic acid	Organic acids
X15	5.58	C₇H₆O₂	4.3	121.0295	121.0302	50808	92.0266, 77.0403	p-Hydroxybenzaldehyde	Phenols	[14]
X16	5.64	C₉H₈O₄	0.9	179.0350	179.0352	80360	134.0371, 108.0214, 93.0345, 89.0401, 79.0555	Caffeic acid	Organic acids	[13]
X17	5.99	C₈H₈O₄	3	167.0350	167.0355	275549	123.0454, 79.0570	Vanillic acid	Organic acids	[12]
X18^b	7.31	C₁₉H₂₈O₁₂	0.4	447.1508	447.1510	14270	269.1028, 233.0656, 161.0449, 101.0242, 71.0153	Gastrodin A	Glycosides	[12]
X19	7.68	C₁₇H₁₉N₅O₅	−1.6	372.1313	372.1307	2202	336.1054, 266.0867, 134.0467	p-Hydroxybenzyl adenosine	Nitrogen-containing compounds
X20	7.73	C₈H₈O₃	0.5	151.0401	151.0402	7660	136.0155, 108.0219, 92.0273	Vanilline	Phenols
X21	8.62	C₁₇H₂₀O₉	−0.7	367.1035	367.1032	21071	193.0496, 191.0553, 173.0455, 134.0369, 111.0463, 93.0349, 85.0299	3-Feruloylquinic acid	Organic acids	[16]
X22	8.94	C₉H₁₀O₃	−0.8	165.0557	165.0556	2085	119.0515, 103.0604	L-(-)-Phenyllactic acid	Organic acids
X23^b	9.11	C₃₂H₄₀O₁₉	4.9	727.2091	727.2151	122722	459.1156, 441.1045, 423.0937, 397.1142, 369.1188, 217.0496	Parishin B	Glycosides	[13]
X24	9.78	C₃₃H₄₂O₂₀	4	757.2197	757.2227	659	503.1631, 453.0961, 161.0480	Parishin H or M	Glycosides	[12]
X25	10.00	C₁₀H₁₀O₄	0.7	193.0506	193.0508	97733	178.0265, 149.0591, 134.0372	Ferulic acid	Organic acids	[13]
X26	10.02	C₂₁H₂₈O₁₃	0	487.1457	487.1457	4684	441.0958, 423.0934, 397.1169, 161.0430, 111.0091	Parishin O or N	Glycosides	[12]
X27	10.05	C₃₂H₄₀O₁₉	4.9	727.2091	727.2127	122722	459.1156, 441.1045, 423.0937, 397.1142, 369.1188, 161.0453	Parishin C	Glycosides	[12]
X28	10.71	C₁₄H₁₄O₃S	−2.2	261.0591	261.0585	777	205.8269, 167.8694, 137.0057	4,4′-Dihydroxybenzyl sulfoxide	Phenols	[14]
X29	11.74	C₁₁H₁₂O₅	−2.2	223.0612	223.0607	2431	108.0226, 179.0713	Sinapic acid	Organic acids	[13]
X30	12.20	C₇H₆O₃	2.5	137.0244	137.0248	31464	108.0215, 93.0352, 65.0410	p-Hydroxybenzoic acid	Phenols	[14]
X31	13.21	C₄₅H₅₆O₂₅	4.7	995.3038	995.3107	39727	727.2129, 441.1065, 423.0915, 397.1119, 161.0457	Parishin	Glycosides	[12]
X32	13.56	C₂₀H₂₄O₈	0.2	391.1398	391.1399	6858	229.0860, 123.0452, 121.0288, 107.0511, 93.0357, 71.0265	Bis-(4-hydroxybenzyl)-ether-mono-β-D-glucopyranoside	Glycosides	[14]
X33	13.69	C₂₆H₃₀O₁₄	2.9	565.1563	565.1579	811	177.0188, 111.0153	Parishin W	Glycosides	[12]
X34	14.13	C₂₅H₂₄O₁₂	2.6	515.1195	515.1208	91406	353.0879, 335.0781, 191.0558, 179.0345, 173.0450, 161.0240	3,4-Dicaffeoylquinic acid isomer	Organic acids	[15]
X35	16.48	C₂₅H₂₄O₁₂	2.6	515.1195	515.1208	91406	353.0879, 335.0781, 191.0558, 179.0345, 173.0450, 161.0240	3,4-Dicaffeoylquinic acid isomer	Organic acids	[15]
X36	17.42	C₉H₁₂O₂	−0.8	151.0765	151.0763	1891	133.0677, 107.0520, 94.0274, 77.0394	4-(Ethoxymethyl)phenol	Phenols	[14]
X37	23.89	C₁₄H₁₄O₂S	−4	245.0642	245.0632	2498	139.0217	Bis(4-hydroxybenzyl)sulfide	Phenols	[14]
X38	32.90	C₉H₈O₃	−1	163.0401	163.0399	4130	145.0279, 135.0455, 119.0493, 91.0184, 77.0443, 65.0039	p-Hydroxycinnamic acid	Organic acids
X39	39.73	C₁₆H₂₂O₄	−0.2	277.1445	277.1445	5380	233.1544, 206.8262	Dibutyl phthalate	Phenols
Peak	RT (min)	Formula	Error (ppm)	[M+H]⁺ (m/z)		Intensity	Product ions	Identification	Structure class	Ref.
Peak	RT (min)	Formula	Error (ppm)	Calculated	Measure	Intensity	Product ions	Identification	Structure class	Ref.
Y1^a,b	1.05	C₅H₅N₅	−1.8	136.0618	136.0615	46698	nd	Adenine	Nitrogen-containing compounds
Y2	1.08	C₁₀H₁₃N₅O₄	1.5	268.1040	268.1044	174357	136.0623, 119.0360,	Adenosine	Nitrogen-containing compounds
Y3^b	1.09	C₉H₁₁NO₃	−1.9	182.0812	182.0808	34675	nd	Tyrosin	Nitrogen-containing compounds
Y4	8.60	C₂₄H₂₉N₃O₈S	−0.5	520.1748	520.1746	7896	308.0836, 285.0913, 233.0591, 179.0486, 162.0208, 107.0485	(2)-g-L-[N-(4-Hydroxy benzyl)]glutamyl-L-[s-(4-hydroxybenzyl)] cysteinylglycine	Nitrogen-containing compounds
Y5	9.77	C₁₀H₈O₄	−0.8	193.0495	193.0494	14081	178.0257, 150.0323, 133.0281, 122.0361	3-Carboxyethyl-phthalide	Organic acids	[16]
Y6	10.55	C₁₂H₁₈O₅	−0.1	243.1227	243.1227	13011	165.0909, 151.0381, 137.0949	3-Butyl-3-hydroxy-4,5,6,7-tetrahydro-6,7-dihydroxy phthalide	Organic acids
Y7	10.55	C₁₂H₁₆O₄	−0.5	225.1121	225.1119	21174	207.1023, 165.0557, 151.0376, 137.0954	Senkyunolide H or I or ligustilidiol or cis-6,7-dihydroxy-ligustilide	Phthalides	[9]
Y8	11.94	C₁₂H₁₆O₅	−0.8	241.1071	241.1069	1918	150.0677, 107.0497, 71.0498	Senkyunolide R or S	Phthalides
Y9	13.27	C₁₂H₁₆O₃	0.1	209.1172	209.1172	288915	153.0544, 149.0593, 135.0473, 121.1006, 117.0709	Senkyunolide G or K or Z-6,7-epoxyligustilide	Phthalides	[9]
Y10	13.27	C₁₂H₁₈O₄	0.4	227.1278	227.1279	102387	163.1104, 153.0543, 149.0961, 119.0860, 107.0484, 79.054	Senkyunolide J or N or R2	Phthalides	[9]
Y11	16.56	C₁₂H₁₄O₃	−0.6	207.1016	207.1015	1327567	189.0917, 165.0550, 146.0732, 133.0653, 119.0841, 105.0693	3-Butylidene-6-hydroxy-5,6-dihy-drophthalide or senkyunolide F or chuanxiongol	Phthalides	[9]
Y12	16.57	C₁₂H₁₆O₄	−0.9	225.1121	225.1119	39845	165.0533, 133.0658, 128.0619, 91.0532, 77.0402	Senkyunolide H or I or ligustilidiol or cis-6,7-dihydroxy-ligustilide	Phthalides	[9]
Y13	17.87	C₁₂H₁₄O₄	−0.2	223.0965	223.0966	23855	177.0921, 149.0591, 121.0308, 103.0523, 77.0401	Senkyunolide D or 4,7-dihydroxy-3-butylphthalide	Phthalides	[9]
Y14	18.08	C₁₂H₁₄O₃	−0.1	207.1016	207.1015	425060	189.0901, 165.0558, 161.0948, 128.0620, 105.0701, 91.0549, 77.0393	3-Butylidene-6-hydroxy-5,6-dihy-drophthalide or senkyunolide F or chuanxiongol	Phthalides	[9]
Y15	19.53	C₁₈H₂₈O₈	0.3	373.1857	373.1858	45450	211.1335, 193.1228, 147.1172, 105.0702, 79.0577	Ligusticoside A	Glycosides	[17]
Y16	21.97	C₁₂H₁₂O₂	−0.5	189.0910	189.0910	151946	128.0623, 115.0544, 105.0702, 91.0551, 77.0388	Butylidenephthalide isomer	Phthalides	[9]
Y17	23.67	C₁₂H₁₄O₄	0.3	223.0965	223.0966	43428	177.0899, 167.0387, 149.0227, 121.0278, 91.0541, 77.0382	Senkyunolide D or 4,7-dihydroxy-3-butylphthalide	Phthalides	[9]
Y18	24.29	C₁₂H₁₂O₂	0	189.0910	189.0910	305525	152.0611, 128.0618, 115.0529, 105.0341, 91.0537, 77.0394	Butylidenephthalide isomer	Phthalides	[9]
Y19	24.50	C₁₂H₁₄O₂	−0.9	191.1067	191.1067	340079	117.0688, 91.0560, 77.0396	3-Butylphthalide or Z-ligustilide or E-ligustilide	Phthalides	[9]
Y20	26.27	C₁₂H₁₅ClO₃	−0.5	243.0783	243.0781	21244	207.1020, 189.0907, 161.0364, 133.0640, 119.0840, 91.0533,	Senkyunolide L	Phthalides	[18]
Y21	26.63	C₁₂H₁₂O₃	0.6	205.0859	205.0860	90627	187.0745, 168.0574, 144.0573, 131.0493, 115.0541, 103.0552, 91.0533, 77.0401	Senkyunolide B or C	Phthalides	[9]
Y22	27.74	C₁₃H₁₆O₃	−0.6	221.1172	221.1171	4804	175.1090, 105.0691	2-(1-Oxopentyl)-benzoic	Organic acids
Y23	27.90	C₁₂H₁₂O₃	0.6	205.0859	205.0860	90627	187.0745, 168.0574, 144.0573, 131.0493, 115.0541, 103.0552, 91.0533, 77.0401	Senkyunolide B or C	Phthalides	[9]
Y24	28.65	C₁₂H₁₆O₂	0.7	193.1223	193.1225	2273337	147.1167, 137.0590, 119.0498, 105.0699, 91.0544, 77.0389, 65.0383	Senkyunolide A	Phthalides	[9]
Y25	29.49	C₁₂H₁₄O₂	0.3	191.1067	191.1067	3489472	153.0704, 145.1007, 135.0440, 117.0695, 91.0546, 77.0391	3-Butylphthalide or Z-ligustilide or E-ligustilide	Phthalides	[9]
Y26	32.06	C₁₂H₁₂O₂	−0.5	189.0910	189.0910	39396	152.0611, 128.0615, 115.0545, 91.0554	Butylidenephthalide isomer	Phthalides	[9]
Y27^b	32.89	C₁₂H₁₈O₂	−0.8	195.1380	195.1378	686098	177.1344, 149.1309, 79.0550	Cnidilide or neocnilide	Phthalides	[9]
Y28	33.04	C₁₂H₁₄O₂	0.3	191.1067	191.1067	637725	173.0961, 145.1008, 130.0773, 117.0694, 91.0548, 77.0392	3-Butylphthalide or Z-ligustilide or E-ligustilide	Phthalides	[9]
Y29	33.64	C₁₂H₁₂O₂	−0.2	189.0910	189.0910	401466	152.0627, 128.0622, 115.0540, 91.0550	Butylidenephthalide isomer	Phthalides	[9]
Y30	35.24	C₁₂H₂₀O₂	−0.7	197.1536	197.1535	21102	119.0862, 95.0856, 91.0555, 81.0697, 67.0552,	3,7-Dimethyl-3-acetate-1,6-octadiene-3-ol acetate	Others
Y31	36.15	C₂₁H₃₂O₂	0.9	317.2475	317.2478	12477	281.2253, 211.1524, 187.1501, 159.1179, 149.1329, 145.0997, 117.0717, 81.0720	Pregnenolone	Others
Y32	36.37	C₂₄H₂₈O₅	0.1	397.2010	397.2010	71592	191.1064, 173.0954, 155.0852, 145.1003, 128.0625, 117.0715, 105.0724, 91.0544	Chuanxiongnolide A or B	Others	[19]
Y33	38.22	C₂₄H₂₈O₅	0.4	397.2010	397.2010	66600	361.1802, 333.1842, 307.1708, 291.1401, 279.1403, 261.1264,2 17.0999, 191.1070, 173.0972, 91.0553	Chuanxiongnolide A or B	Others	[19]
Y34	39.08	C₂₄H₃₂O₅	−0.4	401.2323	401.2321	20533	383.2246, 191.1061, 163.1084, 149.0594, 145.1037, 135.0439	Chuanxiongdiolide R2 or chuanxiongdiolide B	Others	[20]
Y35	39.48	C₁₇H₂₄O₄	0.8	293.1747	293.1750	22471	175.1115, 151.0754, 137.0605, 111.0415, 91.0547, 83.0488	Senkyunolide M or Q	Phthalides	[9]
Y36	41.42	C₂₄H₃₀O₄	−0.1	383.2217	383.2217	1160225	191.1068, 173.0958, 163.1120, 149.0601, 135.0440, 91.0546, 79.0566	Senkyunolide P or 3,8-dihydro-diligustilide or angelicide or Z,Z′−3,3′ −8,8′-diligustilide	Phthalides	[9]
Y37	41.52	C₂₄H₃₂O₄	0.1	385.2373	385.2374	627373	367.2247, 349.2092, 321.2178, 293.1915, 193.1229, 175.1113147.1159, 137.0587, 119.0871, 93.0687	Chuanxiongdiolide A	Others	[20]
Y38	41.88	C₂₄H₂₈O₄	0.1	381.2060	381.2061	4796897	191.1070, 173.0955, 163.1126, 149.0596, 135.0437, 91.0551, 79.0549	Levistolide A or senkyunolide O or tokinolide B or riligustilide	Phthalides	[9]

^a“X” in negative ion mode and “Y” in negative-positive mode. ^bCompared with reference standards.